Water-soluble dyestuffs of the naphthoquinone-imine series and a process of making same



Patented May 15, 1951 UNITED STATES ETNT OFFICE WATER-SOLUBLE DYESTUFFS OFUJTHE NAPHTHOQUINONE-IMINE SERIES :AND

A PROCESS or MAKINGSAME Valentin Kartaschoff,

e Sw tzer and a signor to Sandoz Limited, Basel, SWitrerland,v

a Swiss firm ,No Drawing. Application June 22, 1948, Serial No. 34,554. In Switzerland July 15, 1947 wherein 3: stands for an amino or hydroxy group and at least one of the ys stands for a halogen atom, the other ysbeing. hydrogen. The said naphthoquinone-iminestcan be prepared according to the processes described in applicants copending application\Ser. Nox729/il, filed Feb. ruary 18, 1947, now abandoned and Ser. No. 34,553, filed, June 22, 1948, now Patent No.

As-aromatic; amino compounds there are pref- :erably used the ;sulphonicv and ;;carboxylic acids of the benzene landrnaphthalene series that may containfurther :substituents. The: condensation of the naphthoquinone derivatives-with th -,aro- -matic amino; compounds is preferably carried out inzwaterqin thespresence of a- -solvent, such as -an alcohol, and iin,,.;,th,e, presence of acidbinding a ents at-aa e vate t mp ra urethe case Where the starting products are used inleucoor hydro-form the condensation will be carried out in an inert atmosphere and the condensation products thusobtained will be subsequently oxidised, for example by means of an air stream, preferably in the presence of a base,

such as pyridine, piperidine, ethanolamine or the like.

The condensation products obtained according to the present process ,are;soluble;-i n;.water with raired, 'violet to lblue...co1or.ati9n,and,- dye-an ma '2 fibres in violet-bluerto grey;shades. The .dyeings thus obtained can be after-chromed or aftercoppered. Some of thenemdyestufis canbedyed by the so-called :meta-chromedying process'. 5 The yeings obtained @with the tneWHdyeStll S possess generally good Wetproperties and are stable to the carbonisation treatment. The followingexamples illustrate .howflthe in.- vention can be carried out in practice, but are by no means limitati-ye.

12 grams "of ,sulphanili acid 17 1. so ve i 0.- ramse Wa e th th .10 ram o s dium-p rmeate- I 1 .th ss are a d dz s ca s-o s diume etatew ,60 grams Q Q O y al oho T ithismi added ith 0QdJ1 ti Tn nee room t mp atur 17.2 grams of af finely; powdered ,brominated 20 naphthoguinone-irnine --deriv,atiye containing 4.6% of bromin lenfl 9% of i rq e Example :2

A homogeneous mixture consisting of 240 grams of water, grams of .;S,Qcla.,.;39 grams of J-acid (93. 2,%) grams of sodiumacetate, 480 grams of isopropylalcohol and 51 .6 grams of the naphthoqninone-imine derivative used in EX- ample l-isheated under reflux with good stirring for 20 hours atf C. After thistime the isopropyl alcohol is distilled off, the :charge diluted to 1000 cc. and treatedwith Soda until alkaline to Brilliant Yellow paper. -The-solutidnthds obtained is filtered while still hot and the dyestuff salted out. It is solublein water with a blue coloration.

In place @of the J -acid; in E;xample 2 andpf the sulianilic acid in the Example 1, other 'watersoluble aromatic amino compounds can be used. 5o The efiects producedibydyeing wool, with the respective condensation products obtained with the same 3,7-dibrorno--amino-8-hydroxy-l,4- naphthoquinone-imine-(l) can be seen in the following table:

Shade Arojmatic Anrllino Aftor- Metachromed chromed sulphanilic acid grey-blue grey grey. p-aminosalicylic acid re d dis h red d ishbluish-grey.

blue. grey.

2 amino -1 phenol 4 suldull violet. n e u t r 2.1 grey.

phonic acid. grey.

2 amino 1 phenol -4 sulhhie grey Do.

pho 3 carboxylic acid.

4 81%1110 6 sulphosalicylic do grey-blue. grey-blue.

dehydrothiotoluidine sulgreenish grey-- grey.

phonic acid. grey.

1,6- and 1,7-naphthylaminegrey-blue. do Do.

sulphonic acid.

1,8-naphthylan1ine-sulphondo do Do.

ic acid. 7

l,5 -naphthylamine-sulphondo do Do.

1c ac 2,6-naphthylamine-sulphon do do Do.

ic acid.

l amino 2 naphthol 4 reddishbrown- Do.

sulphonic acid. blue. grey.

1 amino 8 naphthol 4 violet... bluish grey Do.

sulphonic acid.

2-amino-5-naphthol-7- reddishreddish- Do.

sulphonic acid. blue. grey.

2 amino 8 naphthol 6 do grey bluish grey.

sulphonic acid.

1 amino 8 naphthol 3,6 blue do Do.

disulphonic acid. 7

2 -amino -8 -naphtho1-3,6 do greenish Do.

disulphonic acid. grey.

Ewa'mple 3 13 grams of J-acid (47% paste) are dissolved in 40 grams of water with addition of 5 grams of sodium carbonate. To this solution are added grams of sodium acetate, 80 grams of isopropyl alcohol and 8.6 grams of a halogenated naphthoquinone-imine containing 48.5% of bromine and 3.65% of nitrogen and corresponding to formula 2, hereinafter set forth. The charge is then heated with good stirring for 20 hours under reflux at 80 C. After isolation of the dyestuff in the manner described in the above Example 1 it is soluble in water with'ared-violet coloration. It dyes wool in violet shades which become reddishgrey on after-chroming. When dyed according to the metachrome process it gives grey shades. 7

As starting product, i. e. halogenated naphthoquinone-imines, that can be used for the manufacture of the new water-soluble dyestuffs, in place of the halogenated naphthoquinone-imines of the formulas l and 2 employed in Examples 1, 2 and 3:

OH NH the following ones may be used:

OH NH (311 NH OH NH Br Br $11 6 What I claim is:

1. A process for the manufacture of new watersoluble dyestufis of the naphthoquinone-imine series comprising the step of heating a halogenated naphthoquinone-imine of the general formula 0H NH wherein :1: stands for a substituent selected from the group consisting of amino and hydroxy groups and wherein at least one :1; stands for halogen, the other ys being hydrogen, with a water-soluble aromatic amine in presence of a diluent and an acid binding agent.

2. A process for the manufacture of new watersoluble dyestuffs of the naphthoquinone-imine series comprising the step of heating a halogenated naphthoquinone-imine of the general formula OH NH wherein 1: stands for a substituent selected from the group consisting of amino and hydroxy groups and wherein two of the ys stand for halogen, the other two ys being hydrogen, with a water-soluble aromatic amine in presence of a diluent and an acid binding agent.

3. A process for the manufacture of new watersoluble dyestuffs of the naphthoquinone-imine series comprising the step of heating a halogenated naphthoquinone-imine of the general formula wherein x stands for a substituent selected from the group consisting of amino and hydroxy groups and wherein each y stands for halogen, with a Water-solub1e aromatic amine in presence of a diluent and an acid binding agent.

4. A process for the manufacture of new water soluble dyestuffs of the naphthoquinone-imine series comprising the step of heating a halogenated naphthoquinone-imine 0f the general formula OH NH wherein m stands for a substituent selected from the group consisting of amino and hydroxy groups, with a Water-soluble aromatic amine in presence of a diluent and an acid binding agent.

5. A process for the manufacture of new Watersoluble dyestuffs of the naphthoquinone-imine series comprising the step of heating a halogenated naphthoquinone-imine of the formula with an equimolecular quantity of a water-s01- uble aromatic amine in the presence of a diluent and an acid binding agent.

6. The process for the manufacture of a new water-soluble dyestuff of the naphthoquinoneimine series, comprising the step of heating the halogenated naphthoquinone-imine of the formula with an equimolecular quantity of 1 aminonaphtha1ene-8-sulphonic acid in the presence of a diluent and an acid binding agent.

7. The process for the manufacture of a new Water-soluble dyestuff. of the naphthoquinoneimine series, comprising the step of heating the halogenated naphthoquinone-imine of the formula with an equimolecular quantity of 1-amino-8- hydroxy-naphthalene-3,6-disu1phonic acid in the presence of a diluent and an acid binding agent.

9. A compound corresponding to the formula NH- R NHg g wherein NHR stands for the radical of a water-soluble aromatic amine.

10. The compound of the formula 11. The compound of the formula 0H I| IH Br SOaH NHa 'HO VALENTIN KARTASCHOFF.

No references cited. 

1. A PROCESS FOR THE MANUFACTURE OF NEW WATERSOLUBLE DYESTUFFS OF THE NAPTHOQUINONE-IMINE SERIES COMPRISING THE STEP OF HEATING A HALOGENATED NAPTHOQUINONE-IMINE OF THE GENERAL FORMULA 